Textile treating process



Patented Mar. 30, 1943 Tnxmr. TREATING raocnss John B. Rust, Verona, N. 1., aslimor to Ellis- Foster Company, a corporation of New Jersey No Drawing. Application May 5, 1942, Serial No. 441,811

s Claims. (01. 117-167) The present invention relates to a process of making water repellent textiles. An aim of the invention is to employ the water soluble reaction products described in my copending application Serial-Number 392,937, filed May 10, 1941, now Patent No. 2,285,948, granted June 9, 1942., These products are formed by heating together a fatty acid nitrlle containing a carbon chain of more than 9 carbon atoms with a fatty acid chloride containing a carbon chain of more than 9 carbon atoms and paraforxnaldehyde followed by reaction with a tertiary amine.

It has been found that by impregnating a textile fabric such as cotton, linen, viscose, acetate, wool or silk with a solution of the above described reaction products, thereafter drying the impregnated fabric and heating at an elevated temperature excellent water repellent characteristics are imparted to the fabric. By carrying out this process the product becomes fixed upon the fabric to such an extent that it is fast to washing and dry cleaning. In contrast with present known processes involving the development of water repellency by heating a fabric in the presence of compounds such as quaternary ammonium compounds, the present process does not result in a serious decrease in tensile strength of the fabric.

A fabric being so treated cannot be described as waterproof since it will readily wet out in warm water or cold water containing a wetting agent. However, when the fabric is dry it strongly repels water impinging on its surface It has been found that a 1% to 10% solution of the water soluble reaction products'is satisfactory for impregnating purposes. After squeezing out the excess impregnating solution the fabric is dried at, for instance, about 60 C. for 15 to 20 minutes or at 100-110 C. for 1 to 2 minutes in a current of air. By this treatment the fabric is thoroughly dried. It is then heated to a higher temperature 1 of, for instance, 140145 C. for about 15 minutes or at 160-165 C. for from 2 to 5minutes, or even at 170 C. for 1 minute. This latter treatment fixes the fatty acid nitrile-fatty acid chloride-formaldehyde refabric a cut ofl section was dry cleaned by tumaction product. on the fabric, rendering it insoluing, the effect appears to last through several standard soap and water washings.

The following examples are given to illustrate the process of the present invention. All proportions are in parts by weight. V

Example 1.-A reaction product was formed by heating together 137.3 parts of palniityl chloride,

132.7 parts of stearonitriie, 22.5 parts of paraformaldehyde and 1.4 parts zinc chloride for 22 hours at 77 C. followed by reaction with 40 parts'of pyridine at 55 C. for 23 hours. Four parts of this material were dissolved in 20 parts of denatured alcohol and 74 parts of warm water C.) containing 2 parts of sodium acetate trihydrate added. A somewhat'cloudy soapy solution was formed. This solution wasused to impregnate a cotton gabardine fabric which was then squeezed between rubber rollers to remove the excess of solution, dried at 80 C. for 5 minutes and baked at 145 C. for 15 minutes.

In order to test the water repellency of this water and ironed dry. The above two tests will hereinafter be referred to as a "standard dry clean" and "standard wash," respectively. In order to test the degree-of repellency the cloth to be tested was fastened in a 6 inch metal embroidery hoop placed at a 45 angle under a 6 inch glass laboratory funnel to which was attached by a 2 inch rubber tube a spray nozzle. The bottom of the spray nozzle was 6, inches above the surface of the cloth and 250 cc. of water at 80 F. was allowed to flow through the nozzle onto the cloth sample. A rating of 100 was given if no water adhered to the cloth; indicated slight spottin 80 a surface wetting only where the water directly impinged, and 50 a surface wetting of 50% of the area covered by the spray.

The cotton gabardine was subjected .to' these and 2.5 parts of zinc chlorideat 7580 C. for

23 hours followed by reaction with 52.6 parts pyridine at 75 C. for 20 hours. A solution was formed by dissolving parts of the above reaction product in 187 parts of warm water (60 C.) containing 3 parts of sodium acetate trihydrate. A cotton gabardine fabric was impregnated with the solution, squeezed between rubber rollers to removeexcess solution dried at 80 C. and baked at 145 C. for minutes. An

initial spray reading of 80 was obtained. After standard washing a reading of 85, and after standard dry cleaning a reading of 75 was se- 2.7 parts of zinc chloride at 77 C. for'21 hours,

followed byreaction with-37.2 parts of alpha picoline and 7.9 parts of, pyridine at 65-70 ,C. for 21 hours. 173.9 partsof this reactionprodnot were mixed while warmwith an equal weight of dry dioxan and stirred vigorously while coolwas made up by mixing parts of the dioxan paste formed in Example 3 with 177 parts of water at 65 C. containing 3.3 parts of sodium acetate trihydrate. A sample of acetate silk fabric, woolen flannel and-a silk stocking were impregnated with the solution, squeezed free of excess solution, dried at 70"-80 C. and baked at 160 C. for 5 minutes. Cuttings of these treated pieces were also given a standard dry cleaning. The spray readings obtained are given below.

The above examples illustrate the preferred process of the present invention but many variations on the procedure may be made without departing from the spirit of the invention. It

' will also be seen that reaction products of acid ing. A homogeneous smooth paste was formed atroom temperature. A solution was formed by mixing 40 parts of this paste with354 parts of warm wateril (65 C.) containing 6.6 parts of sodiumacetate trihydrate. This solution was used to impregnate cotton gabardine, alight brown dyed mercerized broadcloth having the designation 136 x 72 3.55 and an olive drab dyed mercerized poplinhaving the designation 102 x 56 "2.25. All the cloths were squeezed free of excess solution between rubber. rollers, and dried at 80-90? C. for 10 minutes. They were then baked for varying lengths of time at 160 C. and cuttings given standard dry cleanings. The table below gives the results as obtained on the spray testing device. I

Alter standard dry clean Initial Baking reading sample time M mum Example 4.--35 parts of the reaction product described in Example 3 consisting of mixed palmityl and stearyl chlorides, stearonitrile, paraiormaldehyde, alpha picoline and pyridine (but no dioxan) were ground thoroughlywith 12.5 parts of anhydrous sodium sulfateand 2.5 parts of aluminum distearate. When homogeneous 12 parts of dry dioxan were added to give a stiff paste. A solution was formed by dissolving 12 parts of the above paste in 10 parts of denatured alcohol and adding-175 parts of warm water (65C.) containing 3 parts ofsodium acetate trihydrate. Samples of mercerized poplin (102 1x 56 tion, squeezed, dried and baked at 160 C. for 5 minutes. 'The initial spray readings on both the poplin and'broadcloth vwere 100. After a standard dry cleaning the spray reading on the poplin was 85 and on the broadcloth, 90.

Example '5.-'A slightly cloudysoapy solution 1 t 2.25) and' mercerized broadcloth (136 x 72 4 3,551 were impregnated with the solu- 'filed May 10, 1941.

wax compositions according to chloride, nitrile, paraformaldehyde and tertiary yield the best water repellent effects on treated fabrics. However, in some cases those products containing carbon chains of less than 15 but more than 9 carbon atoms are very satisfactory and yield highly water repellent effects.

To note another instance, very excellent water repellent products may be made by utilizing reaction products of waxes with acid chlorideforming reagents such as the phosphorus chlorides and thionyl chloride in the products of my copendlng application Serial Number 392,937, Such waxes may include montan, candelilla, and the like. These reaction products may be substituted in whole or in part for the acid chlorides in the above products. When textile materials are treated with these the process'of the present invention excellent water repellence is secured with substantially no decreasein the tensile strength of the treated fabric. This is in accordance with the observation that the reaction products of acid chlorides, nitriles and paraformaldehyde in general when used in the process of the present invention do not seriously lower the tensile strength of the treated fabrics. Textile treating compositions prepared from waxes are described in an application of Raymond A. Pingree, Cranston; R. 1., Serial No. 429,400, filed Feb. 3, 1942.

When employing metallic soaps in the process of the present invention it has been found that certain soaps are more satisfactory than others. Among those giving the best results are alumi num distearate, cerium stearate' and lead stearate. 'Other soaps which have been used are aluminum monostearate, aluminum tristearate, barium stearate, aluminum palmitate, calcium stearate, magnesium stearate, strontium stearate and zinc stearate.

be employed such as the diethyl ether of diethylene glycol, methyl acetate, ethyl lactate, the mono methyl ether of diethylene glycol acetate and the like, 1

Although I have given several specific temperatures of drying and baking great variations may be made and higher or lower temperatures employed to secure desirable results.

What I claim is:

1. A process of making textile fabrics water repellent without seriously lowering the tensile strength thereof comprising impregnating a textile fabric with an aqueous solution of from 1% to of a reaction product of a tertiary amine with the compound formed from the reaction of a nitrile containing a chain'of more than 9 carbon atoms, an acid chloride containing a chain of more than 9 carbon atoms and formaldehyde, drying said impregnated textile fabric at below 110 C., and baking said dried impregnated textile fabric between 110 C. and 160 C. for from 1 to minutes.

2. A process of making textile fabrics water repellent without seriously lowering the tensile strength thereof comprising impregnating a textile fabric with an aqueous solution containing 0.1% to 2% of a metallic soap and 1% to 10% of a reaction product of a tertiary amine with the compound formed from the reaction of a nitrfle containing a chain of more than 9 carbon atoms, an acid chloride containing a chain of more than 9 carbon atoms and formaldehyde, drying said impregnated textile fabric at below 110 C., and baking said dried impregnated textile fabric between 110 C. and 160 C. for from 1 to 15 minutes.

3. A process ,of making textile fabrics water repellent without seriously lowering the tensile strength thereof comprising impregnating a textile fabric with an aqueous solution formed by mixing water with 2% to of a paste consisting of between 30% and dioxan and between and 50% of a reaction product of a tertiary amine with the compound formed from the reaction of a nitrile containing a chain of more than 9 carbon atoms, an acid chloride containing a chain of more than 9 carbon atoms and formaldehyde, drying said impregnated textile fabric at below C., and baking said dried impregnated textile fabric between 110 C. and C. for from 1 to 15 minutes.

4. A process of making textile fabrics water repellent without seriously lowering the tensile strength thereof comprising impregnating a textile fabric with an aqueous solution containing 0.1% to 2% of aluminum distearate. and 1% to 10% of a reaction product of a tertiary amine with the compound formed from the reaction of a nitrile containing a chain of more than 9 carbon atoms, an acid chloride containing a chain of more than 9 carbon atoms and formaldehyde, drying said impregnated textile fabric at below 110 C., and baking said dried impregnated textile fabric between 110 C. and 160 C. for from 1 to 15 minutes.

5. A process of making textile fabrics water repellent without seriously loweringthe tensile strength thereof comprising impregnating a textile fabric with an aqueous solution formed by mixing water with 2% to 20% of a paste consisting of between 30% and 50% of an inert water-soluble solvent and between 70% and 50% of a reaction product of a tertiary amine with the compound formed from the reaction of a nitrile containing a chain of more than 9 carbon atoms, an, acid chloride containing a chain of more than 9 carbon atoms and formaldehyde, drying said impregnated textile fabric at below 110 C., and baking said dried impregnated textile fabric between 110 C. and 160 C. for from 1 to 15 minutes.

' JOHN B. RUST. 

